WO2023163573A1 - Catalyseur de synthèse de composé hydrocarboné par réaction directe entre du dioxyde de carbone et de l'hydrogène, procédé de préparation associé et procédé de synthèse de composé hydrocarboné utilisant ledit catalyseur - Google Patents

Catalyseur de synthèse de composé hydrocarboné par réaction directe entre du dioxyde de carbone et de l'hydrogène, procédé de préparation associé et procédé de synthèse de composé hydrocarboné utilisant ledit catalyseur Download PDF

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WO2023163573A1
WO2023163573A1 PCT/KR2023/002822 KR2023002822W WO2023163573A1 WO 2023163573 A1 WO2023163573 A1 WO 2023163573A1 KR 2023002822 W KR2023002822 W KR 2023002822W WO 2023163573 A1 WO2023163573 A1 WO 2023163573A1
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catalyst
cmo
phase
carbon dioxide
reaction
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Korean (ko)
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김재훈
조흔태
칸무하마드
무라마드이라샤
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성균관대학교산학협력단
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Publication of WO2023163573A1 publication Critical patent/WO2023163573A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/398—Egg yolk like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen

Definitions

  • the present invention relates to a catalyst that can be applied to synthesize a hydrocarbon compound through a direct reaction of carbon dioxide and hydrogen, a method for preparing the same, and a method for synthesizing a hydrocarbon compound using the same.
  • Iron (Fe)-based catalysts and cobalt (Co)-based catalysts were mainly used as FTS reaction catalysts that produce alkanes, alkenes, and oxygenates using syngas, which is a mixture of hydrogen (H 2 ) and carbon monoxide (CO). , A number of studies have been conducted on using these catalysts as catalysts for hydrogenation of carbon dioxide.
  • Fe-based catalysts showed similar catalytic performance regardless of whether CO or CO 2 was used as the feed.
  • the RWGS reaction of CO 2 on the Fe 3 O 4 site is promoted through a redox cycle, followed by a continuous FTS reaction on the Fe 5 C 2 site to generate C 5+ hydrocarbons at high yields.
  • GHSV gas hourly space velocity
  • Co-based catalysts are characterized by high chain growth probability (>0.94), high cycle rate, high selectivity to linear paraffins, low WGS reaction activity, high inactivation resistance to water molecules formed during FTS, and high long-term stability. It is very effective for FTS reactions at relatively low temperatures ( ⁇ 240 °C).
  • metallic Co centers When producing long-chain hydrocarbons under typical FTS reaction conditions, metallic Co centers have been considered as the major active sites for the hydrogenation of carbon monoxide, and recently it has been suggested that hydrogenation activity of carbon monoxide on Co 2 C is possible when producing lower olefins. It became.
  • One object of the present invention is a core formed of metal cobalt when exposed to a hydrogen / carbon dioxide mixed gas containing Mn; and a shell formed of a mixture including a Co 3 O 4 phase and a Co 2 C phase on the surface of the core, and when the carbon dioxide hydrogenation reaction proceeds, a high CO 2 of about 60% or more. It is to provide a catalyst for hydrogenation of carbon dioxide capable of achieving a conversion rate and a remarkably high C 5+ hydrocarbon selectivity of about 30% or more.
  • Another object of the present invention is to provide a method for preparing the catalyst.
  • Another object of the present invention is to provide a method for synthesizing a hydrocarbon compound having 5 or more carbon atoms using the catalyst.
  • a catalyst for a hydrogenation reaction of carbon dioxide may be used as a catalyst for promoting a hydrogenation reaction of carbon dioxide, and may include a core including a metal cobalt phase; and a shell located on the surface of the core and including a Co 3 O 4 phase and a Co 2 C phase.
  • the ratio of the number of moles of manganese to the total number of moles of cobalt and manganese in the catalyst [Mn/(Co+Mn)] may be about 3 or more and about 20% or less.
  • the fraction of the metal cobalt phase in the cobalt-containing phase of the entire catalyst may be about 90% or more and less than 100%.
  • the core may include a metal cobalt phase having a crystal phase of a hexagonal close-packed lattice structure, and pores exposing the core to the outside may be formed in the shell.
  • the shell may further include CoO in addition to the Co 3 O 4 as a cobalt oxide phase, and in this case, the [CoO+Co 3 O 4 ]/Co O ratio may be about 1.5 to 1.9. .
  • the area ratio of the Co 2 C phase in the shell may be about 10 to 30%.
  • the shell may further include a manganese-containing phase, and in this case, the manganese-containing phase may include a MnCO 3 phase, Mn 2 O 3 and Mn 3 O 4 .
  • the fraction of the MnCO 3 phase in the manganese-containing phase may be about 90 to 99%.
  • the catalyst may further include a carbon layer located on the surface of the shell.
  • a method for preparing a catalyst for hydrogenation of carbon dioxide is a method of forming a suspension solution by mixing a reaction solution in which a cobalt precursor compound and a manganese precursor compound are dissolved and a precipitant solution in which a basic precipitant is dissolved. Level 1; A second step of aging the suspension solution; A third step of separating powder from the aged suspension solution; and a fourth step of drying and heat-treating the separated powder to form first catalyst powder.
  • the method may further include a fifth step of forming second catalyst powder by reducing the first catalyst powder in a hydrogen atmosphere.
  • the method may further include a sixth step of forming a third catalyst powder by exposing the second catalyst powder to a flow of a mixed gas of carbon dioxide (CO 2 ) and hydrogen (H 2 ). there is.
  • the cobalt precursor and the manganese precursor have a ratio of moles of manganese ions to total moles of cobalt ions and manganese ions in the reaction solution of about 3 to 20%. It may be added to the reaction solution as much as possible.
  • the total concentration of the cobalt precursor and the manganese precursor in the reaction solution may be about 1.5 to 3 mol/L.
  • the basic precipitant may include sodium carbonate (Na 2 CO 3 ).
  • the separated powders in the fourth step may be dried at a temperature of about 90 to 110 ° C and then heat-treated for about 2 to 5 hours under air flow conditions of about 300 to 360 ° C.
  • the first catalyst powder may include a cobalt oxide phase, a manganese oxide phase, and a phase each of which is doped with sodium.
  • the fifth step is performed by supplying hydrogen gas into the tubular reactor at a temperature of 320 to 400 ° C. for 4 to 8 hours after fixing the first catalyst powder in the tubular reactor, and the fifth During the step, the first catalyst powder may be converted into the second catalyst powder comprising a metallic cobalt phase, a cobalt oxide phase and a manganese oxide phase.
  • the sixth step is performed by supplying a mixed gas of hydrogen and carbon dioxide after adjusting the temperature inside the tubular reactor in which the second catalyst powder is fixed to 250 to 300 ° C.
  • the second catalyst powder includes a core formed of metallic cobalt; and the third catalyst powder including a shell formed of a mixture including a Co 3 O 4 phase and a Co 2 C phase on the surface of the core.
  • the pressure inside the tubular reactor may be adjusted to about 3.5 to 5.0 MPa during the sixth step.
  • a mixed gas in which hydrogen (H 2 ) and carbon dioxide (CO 2 ) are mixed at a ratio of about 2.5:1 to 3.5:1 may be supplied into the tubular reactor during the sixth step.
  • a hydrocarbon compound having 5 or more carbon atoms can be produced by inducing a hydrogenation reaction of carbon dioxide by supplying a mixed gas of hydrogen and carbon dioxide into a tubular reactor in which a catalyst is fixed,
  • the catalyst comprises a core comprising a metallic cobalt phase; and a shell located on the surface of the core and including a Co 3 O 4 phase and a Co 2 C phase.
  • the temperature inside the tubular reactor may be adjusted to about 250 to 300 ° C. during the hydrogenation of carbon dioxide.
  • the pressure inside the tubular reactor may be adjusted to about 3.5 to 5.0 MPa during the hydrogenation of carbon dioxide.
  • a mixed gas in which hydrogen (H 2 ) and carbon dioxide (CO 2 ) are mixed at a ratio of about 2.5:1 to 3.5:1 may be supplied into the tubular reactor.
  • the proportion of linear paraffin in the hydrocarbon compound having 5 or more carbon atoms may be about 90% or more and less than 100%.
  • the catalyst according to the present invention includes a core formed of metal cobalt when exposed to a hydrogen/carbon dioxide mixture gas containing Mn together with Co; and a shell formed of a mixture including a Co 3 O 4 phase and a Co 2 C phase on the surface of the core.
  • FIG. 1 is a flow chart for explaining a method for preparing a cobalt-manganese composite catalyst according to an embodiment of the present invention.
  • FIG. 2 is a view for explaining a catalyst synthesized according to the method shown in FIG. 1 .
  • Figure 4a is a CO 2 conversion rate and products according to the reaction time on the CMO-0 catalyst and the CMO-10 catalyst under pressure conditions of 1.0 MPa (A, B), 2.0 MPa (C, D), and 3.0 MPa (E, F) Graphs showing the results of measuring selectivity
  • FIG. 4b is CO 2 as a function of reaction time on CMO-0, CMO-10, CMO-25, CMO-50, CMO-75, and CMO-100 catalysts at 4.0 MPa. These are graphs showing the results of measuring conversion rate and product selectivity.
  • Figure 5a is a graph showing the results of measuring the CO 2 conversion rate and product selectivity according to the reaction pressure of the CMO-0 catalyst (A) and the CMO-10 catalyst (B), and Figure 5b is a graph showing the reaction time of the CMO-10 catalyst It is a graph showing the results of measuring the CO 2 conversion rate and product selectivity.
  • FIG. 6 is graphs showing the results of measuring the CO 2 conversion rate and product selectivity according to the reaction temperature (A) of the CMO-10 catalyst, the H 2 /CO 2 ratio of syngas (B), and GHSV (C).
  • FIG. 7a shows XRD patterns measured in fresh, reduced, and spent states of CMO-0 and CMO-10 catalysts, respectively
  • FIGS. 7b and 7c show CMO-0, CMO- 10, CMO-25, CMO-50, CMO-70 and CMO-100 catalysts in fresh state (A, B, C) and reduced state (D, E, F) respectively
  • the measured XRD patterns are shown, and FIG.
  • FIG. 7d shows the XRD patterns measured in the spent state of each of the CMO-0, CMO-10, CMO-25, CMO-50, CMO-70 and CMO-100 catalysts
  • Figure 7e shows XRD patterns measured for CMO-10 catalysts converted at 230 °C, 250 °C, 270 °C, 290 °C, and 310 °C, respectively.
  • Figure 8a shows Co K-edge XANES spectra for CMO-y catalysts after reduction (A) and converted CMO-y catalysts (B), and Figure 8b shows Co K-edge XANES profiles evaluated from linear combination fitting.
  • 8c is a graph showing the relationship between metallic Co content and C 5+ hydrocarbon yield
  • FIG. 8c is a relationship between surface carbide content and C 5+ hydrocarbon yield evaluated from C 1s XPS spectrum (D) and [CoO +CO3O4]/CoO and the graph showing the relationship (E) between the C 5+ hydrocarbon yield
  • FIG. 9a shows normalized Co K-edge XANES spectra measured for a converted CMO-0 catalyst (A) and a converted CMO-10 catalyst (B) at various reaction pressures (1 MPa, 2 MPa, 3 MPa, 4 MPa), respectively.
  • D Co K-edge XANES spectra measured for the converted CMO-10 catalyst, respectively, and FIG.
  • 9c shows various GHSV (4000 mL g -1 h -1 , 8000 mL g -1 h -1 , 12000 mL g -1 h - 1 ) and after various reaction times (120 hr, 1440 hr) Co K-edge XANES spectra measured for the converted CMO-10 catalyst, respectively.
  • k 3 -weighted Fourier transforms, FTs k 3 -weighted Fourier transforms, FTs
  • A k 3 -weighted Fourier transform
  • B CMO-10 catalyst converted at 290°C fitted only with metallic Co
  • C metallic Co
  • D Filtered K 3 -weighted ⁇ (k) spectra of CMO-10 catalyst (D) converted at 310 °C fitted with CoO are shown .
  • Figure 11 shows the normalized Mn K-edge XANES spectra of the CMO-y catalyst (A) and the converted CMO-y catalyst (B) after reduction.
  • FIG. 14a is a diagram showing FE-SEM images (A, B), HR-TEM images (C, D), and particle size distribution (E) of the CMO-0 catalyst before reduction, and FIG. HAADF-STEM image of 0 catalyst (F) and its corresponding Co (G); O (H); C (I); Na(J); Co and O (K); It is a diagram showing EDX images of Co, C and O (L).
  • FIG. 15a is a view showing FE-SEM images (A, B), HR-TEM images (C, D), and particle size distribution (E) of the CMO-10 catalyst before reduction, and FIG. HAADF-STEM image of 10 catalyst (F) and its corresponding Co (G); O (H); C (I); Mn (J); Na(K); Co and O (L); It is a diagram showing EDX images of Co, C and O (M).
  • 16a is a diagram showing FE-SEM images (A, B), HR-TEM images (C, D), and particle size distribution (E) of the CMO-0 catalyst after reduction, and FIG. HAADF-STEM image of 0 catalyst (F) and its corresponding Co (G); O (H); C (I); Na(J); Co and O (K); It is a diagram showing EDX images of Co, C and O (L).
  • Figure 17a is a diagram showing FE-SEM images (A, B), HR-TEM images (C, D), and particle size distribution (E) of CMO-10 catalyst after reduction
  • Figure 17b is a diagram showing CMO-10 catalyst after reduction HAADF-STEM image of 10 catalyst (F) and its corresponding Co (G); O (H); C (I); Mn (J); Na(K); Co and O (L); It is a diagram showing EDX images of Co, C and O (M).
  • FIG. 18a shows HR-TEM images (A-C, E) and FFT images (D) of the converted CMO-0 catalyst
  • FIG. 18B shows HAADF-STEM images (F) of the converted CMO-0 catalyst and the corresponding Co ( G); O (H); C (I); Co and O (J); Co, O and C (K); and EDX images of Na (L)
  • FIG. 18C shows Co (M); Co and O (N); Shows the enlarged outermost shell layer of Co, O and C(O).
  • FIG. 19a shows HR-TEM images (A-C, E) and FFT images (D) of the converted CMO-10 catalyst
  • FIG. 19B shows HAADF-STEM images (F) of the converted CMO-10 catalyst and the corresponding Co ( G); O (H); C (I); Mn (J); Co, Mn and O (K); and EDX images of Co, Mn, C, and O (L)
  • FIG. 19C shows Co (M); Co and O (N); Shows the enlarged outermost shell layer of Co, O and C(O).
  • Figure 23a shows SEM, HR-TEM and FFT images of the converted CMO-10 catalyst converted under reaction temperature conditions of 230 °C (A), 250 °C (B), 290 °C (C) and 310 °C (D)
  • Figure 23b is HR-TEM of the converted CMO-10 catalyst converted under reaction temperature conditions of 230 °C (A), 250 °C (B), 270 °C (C), 290 °C (D) and 310 °C (E, F) represent images.
  • FIG. 26a shows the H 2 -TPR profile for the CMO-y catalyst before reduction heat treatment at 330 ° C
  • FIGS. 26b to 26d show the CO 2 -TPD profile, CO-TPD profile and H 2 of the CMO-y catalyst after reduction. -Indicates each TPD profile.
  • 29A-29C show in situ DFIFT CO adsorption profiles on CMO-0 catalysts.
  • 31A and 31B show QMS profiles of products released from the DRIFT cell during H 2 flow over CMO-O catalyst (A), CMO-10 catalyst (B) after CO pressurization to 3.0 MPa and temperature rise to 270 °C. indicate
  • 32A to 32C show reaction profiles of in situ DFIFT CO 2 and H 2 over CMO-0 catalyst after reduction.
  • 33A to 33C show reaction profiles of in situ DFIFT CO 2 and H 2 over CMO-10 catalyst after reduction.
  • 34A and 34B show in situ DFIFT CO 2 and H 2 reaction profiles (A) for 60 minutes on CMO-10 catalyst after reduction under varying reaction pressure conditions and CO 2 -adsorbed species, adsorbed Evolution of CO, gaseous CO and CH 4 is shown (B).
  • 35A and 35B show in situ DFIFT CO 2 and H 2 reaction profiles (A) for 60 minutes on CMO-0 catalyst after reduction under varying reaction temperature conditions and CO 2 -adsorbed species, adsorbed Evolution of CO, gaseous CO and CH 4 is shown (B).
  • first and second may be used to describe various components, but the components should not be limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention.
  • FIG. 1 is a flowchart for explaining a method for preparing a cobalt-manganese composite catalyst according to an embodiment of the present invention
  • FIG. 2 is a diagram for explaining a catalyst synthesized according to the method shown in FIG. 1.
  • the method for preparing a cobalt-manganese composite catalyst according to an embodiment of the present invention is a suspension by mixing a reaction solution in which a cobalt precursor compound and a manganese precursor compound are dissolved and a precipitant solution in which a basic precipitant is dissolved.
  • S110 a first step of forming a suspension solution
  • a second step S120
  • a third step S130
  • separating powder from the aged suspension solution
  • the manufacturing method of the cobalt-manganese composite catalyst may further include a fifth step ( S150 ) of forming a second catalyst powder by reducing the first catalyst powder in a hydrogen atmosphere.
  • the manufacturing method of the cobalt-manganese composite catalyst includes exposing the second catalyst powder to a flow of a mixed gas of carbon dioxide (CO 2 ) and hydrogen (H 2 ) to form a sixth catalyst powder.
  • a step S160 may be further included.
  • the cobalt-manganese composite catalyst prepared according to the present invention directly reacts carbon dioxide (CO 2 ) and hydrogen (H 2 ) to produce a hydrocarbon compound, for example, a liquid hydrocarbon compound having 5 or more carbon atoms (C 5+ ). can be used as a catalyst for
  • the cobalt precursor is not particularly limited as long as it is a material capable of providing cobalt (Co) ions to the reaction solution, and may include, for example, cobalt nitride.
  • the manganese precursor compound is not particularly limited as long as it is a material capable of providing manganese ions to the reaction solution, and may include, for example, manganese (Mn) nitride.
  • the cobalt precursor and the manganese precursor are added to the reaction solution so that the ratio of the number of moles of manganese ion to the total number of moles of cobalt ion and manganese ion in the reaction solution is about 3 or more and less than or equal to 20%.
  • the solvent of the reaction solution is not particularly limited as long as it can dissolve the cobalt precursor and the manganese precursor, and for example, water such as deionized water may be used as the solvent.
  • the ratio of the number of moles of manganese ion to the total number of moles of cobalt ion and manganese ion in the reaction solution is about 4 or more and 18% or less, about 5 or more and 15% or less, about 6 or more and about 14% or less, about 7 or more and 13% or less, about 8 or more and 12% or less, or about 9 or more and 11% or less.
  • the total concentration of the cobalt precursor and the manganese precursor in the reaction solution may be about 1 to 5 mol/L.
  • concentrations of the cobalt precursor and the manganese precursor in the reaction solution may be about 1.5 to 3 mol/L.
  • the basic precipitant may precipitate a reaction product of cobalt ions dissociated from the cobalt precursor and manganese ions dissociated from the manganese precursor by adjusting the suspension solution to be basic.
  • a basic compound may be used without limitation.
  • the basic precipitant may include sodium carbonate, for example, sodium carbonate (Na 2 CO 3 ).
  • the solvent of the basic precipitant solution may be the same as the solvent of the reaction solution, and the concentration of the sodium carbonate in the basic precipitant solution may be about 1 to 5 mol/L.
  • the concentration of the sodium carbonate may be about 1.5 to 3 mol/L.
  • the reaction solution and the precipitant solution are mixed in the same solvent as the solvent of the reaction solution and the precipitant solution, respectively, at a temperature of about 20 to 40 ° C. and stirring conditions.
  • the cobalt ions dissociated from the cobalt precursor and the manganese ions dissociated from the manganese precursor may react.
  • the pH of the suspension solution may be maintained at about 7.5 to 8.5.
  • a bright purple precipitate may be formed by dropwise addition of the reaction solution and the precipitant solution.
  • the suspension solution may be aged for about 4 to 10 hours without stirring at about 20 to 40 ° C. after stirring for about 4 to 10 hours in a sealed container.
  • the third step (S130) it is possible to separate the powders produced by the reaction of the cobalt ions and the manganese ions from the aged suspension through centrifugation, and the separated powders are washed using deionized water.
  • Centrifugation conditions for separating the powders are not particularly limited.
  • the separated powders may be dried at a temperature of about 90 to 110 ° C. and then heat-treated for about 2 to 5 hours under air flow conditions of about 300 to 360 ° C.
  • a first catalyst powder containing cobalt oxide and manganese oxide may be formed by heat treatment.
  • the first catalyst powder may include a cobalt oxide phase, a manganese oxide phase, and a phase each of which is doped with sodium.
  • the second catalyst powder may be produced by exposing the first catalyst powder to a flow of hydrogen gas to reduce a part of the cobalt oxide phase of the first catalyst powder to a metallic cobalt phase.
  • the second catalyst powder is a metallic cobalt phase; cobalt oxide phases such as CoO, Co 3 O 4 ; Manganese oxide phases such as MnO, MnO 2 , Mn 2 O 3 , and Mn 3 O 4 may be included. Meanwhile, manganese contained in the first catalyst powder may reduce the reduction reaction of the cobalt oxide phase and inhibit crystal growth of the metallic cobalt phase, and as a result, reduce the entire cobalt oxide phase to the metallic cobalt phase.
  • the metallic cobalt phase may include a hexagonal close-packed lattice structure crystal phase, and may further include a relatively small amount of a face centered cubic lattice structure crystal phase. .
  • the first catalyst powder is exposed to the hydrogen gas flow for about 4 to 8 hours while being heated to about 320 to 400 ° C. at a heating rate of about 1 to 5 ° C after being fixed in a tubular reactor. It may be converted into a second catalyst powder, and at this time, the pressure inside the tubular reactor may be adjusted to about 3.5 to 5.0 MPa. Meanwhile, the first catalyst powder may be mixed with silica powder as a thermal diluent and then fixed inside the tubular reactor by a porous support such as quartz wool.
  • a part of the cobalt oxide phase of the second catalyst powder may be additionally reduced to a metal cobalt phase by hydrogen, and a part of manganese oxide by carbon species generated by decomposition of carbon dioxide.
  • Silver may be converted into manganese carbonate, a cobalt carbide (Co 2 C) phase may be formed on the surface of the metallic cobalt phase, and agglomeration may occur between the second catalyst powders in the process of forming the third catalyst powder.
  • the second catalyst powder includes a core on metal cobalt; and a shell having a porous structure formed on the surface of the core, including a cobalt oxide phase, a cobalt carbide phase, and the like, and having pores exposing a portion of the surface of the core to the outside. It can be.
  • the structure and composition of the third catalyst powder will be described later.
  • the sixth step (S160) is to adjust the temperature inside the tubular reactor to about 250 to 300 ° C. in a state in which the second catalyst powder is fixed in the tubular reactor, and then hydrogen (H 2 ) and carbon dioxide ( It can be performed by flowing a mixed gas (H 2 /CO 2 ) of CO 2 for a certain period of time.
  • the temperature inside the tubular reactor When the temperature inside the tubular reactor is less than 250 ° C, the decomposition reaction of carbon dioxide is weak, and the problem of insufficient production of cobalt metal phase or cobalt carbide phase may occur, and when it exceeds 300 ° C, structural collapse of the third catalyst powder may occur as well as a problem that the methanation reaction of carbon dioxide occurs more predominantly than the RWGS reaction due to the re-oxidation of the metal Co phase caused by the aggregation of the nanoparticles.
  • the temperature inside the tubular reactor may be adjusted to about 270 to 290 °C.
  • the sixth step (S160) hydrogen (H 2 ) and carbon dioxide (CO 2 ) by flowing a mixed gas (H 2 /CO 2 ) for a certain period of time.
  • a mixed gas H 2 /CO 2
  • the pressure inside the tubular reactor in the sixth step (S160) may be adjusted to about 3.5 to 5.0 MPa, the same as or similar to the pressure inside the tubular reactor in the fifth step (S150).
  • a flow of a mixed gas in which hydrogen (H 2 ) and carbon dioxide (CO 2 ) are mixed at a ratio of about 2.5: 1 to 3.5: 1 is formed inside the tubular reactor. It can be.
  • the H 2 /CO 2 ratio is less than 2.5, the amount of metal cobalt formed by reduction of cobalt oxide is small, which may cause a problem of lowering the FTS reaction, and when it exceeds 3.5, the metal Co phase due to aggregation of particles Re-oxidation may cause a problem of lowering the FTS reaction.
  • the mixed gas may be supplied to the tubular reactor at a gas hourly space velocity (GHSV) of about 4000 to 10000 mL g ⁇ 1 h ⁇ 1 .
  • GHSV gas hourly space velocity
  • the catalyst prepared by the above method the core formed on the metal cobalt; and a shell formed of a mixture including a Co 3 O 4 phase and a Co 2 C phase on the surface of the core.
  • the ratio of the number of moles of manganese elements to the total number of moles of cobalt and manganese elements [Mn/(Co+Mn)] may be about 3 or more and about 20% or less.
  • the ratio of the number of moles of manganese to the total number of moles of cobalt and manganese is less than 3%, it is difficult to expect improvement in the chain-growth reaction by the manganese-containing phase. Problems such as a decrease in the degree of carbon dioxide conversion and a decrease in the conversion rate of carbon dioxide may occur due to a decrease in the proportion of the cobalt oxide phase that promotes the direct decomposition reaction of carbon dioxide.
  • the ratio of the number of moles of the manganese element to the total number of moles of the cobalt and manganese elements exceeds 20%, the production of the metallic cobalt phase may be insufficient, and the conversion rate of carbon dioxide may decrease.
  • the ratio of the number of moles of the manganese element to the total number of moles of the cobalt and manganese elements is about 4 or more and 18% or less, about 5 or more and 15% or less, about 6 or more about 14% or less, about 7 or more and 13% or less, about 8 or more and 12% or less, or about 9 or more and 11% or less.
  • the core may include a metallic cobalt phase having a crystal phase of a hexagonal close-packed lattice structure
  • the shell may include a Co 3 O 4 phase containing oxygen vacancies and cobalt carbide. (Co 2 C) phase. Pores exposing the core to the outside may be formed in the shell.
  • the fraction of the metallic cobalt phase in the cobalt-containing phase in the catalyst may be about 90% or more and less than 100%, about 91% or more and 99% or less, or about 92% or more and 98% or less.
  • the shell of the catalyst may further include CoO in addition to Co 3 O 4 as a cobalt oxide phase, and in this case, the [CoO+Co 3 O 4 ]/Co O ratio may be about 1.5 to 1.9. .
  • the area ratio of the Co 2 C phase in the shell of the catalyst may be about 10 to 30%, about 11 to 20%, or about 12 to 17%.
  • the shell may further include a manganese-containing phase.
  • the manganese-containing phase may include a manganese carbonate phase and a manganese oxide phase.
  • the manganese carbonate phase may include a MnCO 3 phase
  • the manganese oxide phase may include Mn 2 O 3 and Mn 3 O 4 .
  • the fraction of the MnCO 3 phase in the manganese-containing phase may be about 90 to 99%, about 91 to 97, or about 92 to 95%.
  • the cobalt oxide containing oxygen vacancies in the shell can improve the activity of a decomposition reaction of carbon dioxide, for example, a reverse water gas shift (RWGS) reaction, and the cobalt carbide phase and the metal cobalt phase are Hydrogenation of intermediate products such as CHO radicals (CHO*) and CO radicals (CO*) generated by the decomposition reaction of carbon dioxide, for example, Fischer-Tropsch Synthesis (FTS), and
  • RWGS reverse water gas shift
  • CO* CO radicals
  • FTS Fischer-Tropsch Synthesis
  • the activity of the chain growth reaction can be enhanced.
  • a decomposition reaction of carbon dioxide may occur at an oxygen vacancy site on cobalt oxide in the shell to produce intermediates of CHO* and CO*, and these intermediates may form adjacent cobalt carbide phases (Co 2 C) and the core. may migrate onto the metal cobalt (Co) phase of hydrogenation and chain growth reactions.
  • a graphitic carbon layer may be additionally formed on the outermost surface of the third catalyst powder, and this carbon layer may contribute to further increasing the activity of the hydrocarbon chain growth reaction.
  • the catalyst may be used as a catalyst for a reaction in which hydrocarbons having 5 or more carbon atoms are formed through hydrogenation of carbon dioxide.
  • a hydrocarbon having 5 or more carbon atoms may be produced by inducing a hydrogenation reaction of carbon dioxide by supplying a mixed gas of hydrogen and carbon dioxide into a tubular reactor in which the catalyst is fixed.
  • a mixture of hydrogen (H 2 ) and carbon dioxide (CO 2 ) (H 2 /CO 2 ) is introduced into the tubular reactor. It can be supplied at a constant rate into the reactor.
  • the temperature inside the tubular reactor When the temperature inside the tubular reactor is less than 250 ° C, the methanation reaction of carbon dioxide predominantly occurs, which may cause a decrease in the yield of hydrocarbons having 5 or more carbon atoms, and when the temperature inside the tubular reactor exceeds 300 ° C In this case, not only structural collapse of the catalyst may occur, but also a problem in that the methanation reaction of carbon dioxide occurs more predominantly due to reoxidation of the metal Co phase caused by the aggregation of nanoparticles.
  • the temperature inside the tubular reactor in which the catalyst is fixed may be adjusted to about 270 to 290°C.
  • the pressure inside the tubular reactor is adjusted to about 3.5 MPs or more, and then the mixed gas (H 2 /CO 2 ) can be supplied into the tubular reactor at a constant rate.
  • the pressure inside the reactor is less than 3.5 MPa, re-adsorption of C 2 to C 4 hydrocarbons may be reduced, resulting in a decrease in the yield of C 5+ hydrocarbons.
  • the pressure inside the tubular reactor may be adjusted to about 3.5 to 5.0 MPa.
  • a mixed gas in which hydrogen (H 2 ) and carbon dioxide (CO 2 ) is mixed at a ratio of about 2.5: 1 to 3.5: 1 may be supplied into the tubular reactor.
  • H 2 /CO 2 ratio is less than 2.5, there may be a problem that the FTS reaction is deteriorated due to insufficient hydrogen, and when it exceeds 3.5, the FTS reaction is caused by re-oxidation of the metal Co phase of the catalyst due to aggregation of particles Deterioration problems may occur.
  • the mixed gas may be supplied to the tubular reactor at a gas hourly space velocity (GHSV) of about 4000 to 10000 mL g ⁇ 1 h ⁇ 1 .
  • GHSV gas hourly space velocity
  • the proportion of linear paraffin among the C5+ hydrocarbons produced using the catalyst may be about 90% or more.
  • the ratio of olefins/paraffins may be less than about 0.5%, and the ratio of oxygenated species may also be extremely low, such as less than about 1%.
  • a Mn-promoted core-shell Co@CoO x /Co 2 C catalyst (CMO-y, where y represents mol% of Mn) was synthesized using a co-precipitation method, and hydrogenation of carbon dioxide was performed using the same.
  • cobalt nitride [Co(NO 3 ) 2 6H 2 O] and manganese nitride [Mn(NO 3 ) 2 4H 2 O] were dissolved in distilled and deionized water at the ratios shown in Table 1 to obtain 2
  • a reaction solution having a concentration of mol/L was prepared, and a precipitant solution was prepared by dissolving sodium carbonate [Na 2 CO 3 ] in deionized water at a concentration of 2 mol/L.
  • 40 mL of the reaction solution and 40 mL of the precipitant solution were added dropwise to 50 mL of deionized water under vigorous stirring conditions at 25 ° C. At this time, the pH of the mixed solution was maintained at 8.0 ⁇ 0.1.
  • a light purple precipitate was formed by dropwise addition of the reaction solution and the precipitant solution.
  • the mixed solution was aged at 25° C. for 6 hours without stirring.
  • the aged mixed solution suspension was centrifuged 4 times with deionized water at 4000 rpm to collect powder, washed with deionized water, and dried at 100° C. for 12 hours.
  • the dried powder was heat-treated at 330° C. under an air flow condition of 100 mL/h for 3 hours to prepare ‘catalyst powder before reduction (hereinafter referred to as ‘CMO-y before reduction’)’.
  • a hydrogen (H 2 ) flow condition of 50 mL/min, a temperature condition of 350 °C with a temperature increase rate of 2.5 °C/min, and a pressure condition of 4.0 MPa were formed in the tubular reactor to form the catalyst powder before reduction. was reduced in advance for 6 hours to prepare 'catalyst powder after reduction (hereinafter referred to as 'reduced CMO-y')'.
  • 'Converted catalyst powder (hereinafter referred to as 'converted CMO-y')' was prepared by exposing the catalyst powder after reduction to a mixed gas for 125 hours, and hydrogenation of carbon dioxide was continuously performed under the same conditions for 1425 hours. .
  • the CMO-10 catalyst with a Na content of 0.12 wt% resulted in a high CO 2 conversion of 64.3%, a significantly high C 5+ selectivity of 32.9% and a significantly low CO of 0.2%. was found to have a selectivity of And the C 5+ hydrocarbon yield of the CMO-10 catalyst was found to be 21.1%, which is significantly higher than that of the conventional Co-based catalyst (0 to 1.4%), as previously reported at GHSV ⁇ 4000 mL g -1 h -1 It was comparable to the reported Fe-based catalyst (11.7 ⁇ 26.4%).
  • the chain growth probability of C 5+ hydrocarbons on the CMO-10 catalyst was 0.74, which was significantly higher than other Co-based catalysts ( ⁇ 0.25).
  • the distribution of hydrocarbons formed on the CMO-10 catalyst was measured as 32.9% of C 5+ hydrocarbons, 44.2% of methane (CH 4 ) and 22.9% of C 2 ⁇ C 4 hydrocarbons, from which the CMO-10 catalyst It was confirmed that gas and liquid fuels can be produced at a high yield through the applied one-pass carbon dioxide stream (CO 2 stream).
  • the one-pass CO 2 conversion rate on the Fe-based catalyst was 40% or less at GHSV ⁇ 4000 mL g -1 h -1 , and showed a high residual CO selectivity of 15% or more. Therefore, in order to construct a carbon dioxide conversion device using an Fe-based catalyst on a practical commercial scale, a wastewater recycling device or an FTS reaction system equipped with a two-stage RWGS and water removal device is required. In contrast, the CMO-10 catalyst exhibits high CO 2 conversion (64.3%), high C 5+ hydrocarbon yield (21.1%), negligible CO selectivity (0.7%), and relatively low temperature (270%). °C), it is evaluated to have a clear advantage over Fe-based catalysts.
  • the chain growth probability on CMO-10 was slightly higher than that on CMO-0 catalyst, and the chain growth probability increased with increasing Mn content in CMO-y catalyst. From this, it can be seen that in the CMO-y catalyst, Mn can perform a function of suppressing the chain termination reaction, so that longer chain hydrocarbons can be formed as the Mn content increases. Specifically, it was confirmed that C 10+ carbon hydrogen was the main species in the hydrocarbons produced on the CMO-75 catalyst.
  • Figure 4a is a CO 2 conversion rate and products according to the reaction time on the CMO-0 catalyst and the CMO-10 catalyst under pressure conditions of 1.0 MPa (A, B), 2.0 MPa (C, D), and 3.0 MPa (E, F) Graphs showing the results of measuring selectivity
  • FIG. 4b is CO 2 as a function of reaction time on CMO-0, CMO-10, CMO-25, CMO-50, CMO-75, and CMO-100 catalysts at 4.0 MPa. These are graphs showing the results of measuring conversion rate and product selectivity.
  • FIG. 6 is a graph showing the results of measuring the CO 2 conversion rate and product selectivity according to the reaction temperature (A) of the CMO-10 catalyst, the H 2 /CO 2 ratio of syngas (B), and GHSV (C). admit.
  • A 4.0 MPa reaction pressure
  • H 2 /CO 2 3: 1 syngas
  • B is a reaction temperature of 270 °C
  • a reaction pressure of 4.0 MPa and GHSV 4000 mL g -1 h -1
  • CO 2 1000 mL g -1 h - 1 ;
  • H2 3000 mL g -1 h -1
  • reaction pressure on CO 2 conversion was found to be greater on the CMO-10 catalyst than on the CMO-0 catalyst, which is believed to be due to the higher reaction pressure and the Mn promoter facilitating the chain propagation reaction more.
  • the methanation activity on the CMO-10 catalyst was increased under high temperature (310 °C), high H 2 /CO 2 ratio (4:1) and high GHSV (12000 mL g -1 h -1 ) conditions. .
  • a similar behavior was observed in the FTS reaction of typical H 2 /CO syngas, and also an increase in methanation activity at high temperature (310 °C) and high H 2 /CO 2 ratio (4:1) was previously reported. similar to the CO 2 conversion on a Co-based catalyst.
  • the CMO-10 catalyst has stability capable of stably converting CO 2 and generating long-chain hydrocarbons for 1425 hours in the hydrogenation of CO 2 .
  • this excellent stability for more than 1425 hours it is judged that the performance of the CMO-10 catalyst is maintained despite sintering of the active site and deposition of polymeric carbon or coke.
  • FIG. 7a shows XRD patterns measured in fresh, reduced, and spent states of CMO-0 and CMO-10 catalysts, respectively
  • FIGS. 7b and 7c show CMO-0, CMO- 10, CMO-25, CMO-50, CMO-70 and CMO-100 catalysts in fresh state (A, B, C) and reduced state (D, E, F) respectively
  • the measured XRD patterns are shown, and FIG.
  • 7d shows the XRD patterns measured in the spent state of each of the CMO-0, CMO-10, CMO-25, CMO-50, CMO-70 and CMO-100 catalysts
  • Figure 7e shows XRD patterns measured for CMO-10 catalysts converted at 230 °C, 250 °C, 270 °C, 290 °C, and 310 °C, respectively.
  • 7a to 7d the catalyst after each reduction was reduced for 6 hours at a pressure of 4.0 MPa, a H 2 flow of 50 mL/min, and a temperature condition of 350° C. (heating rate of 2.5° C./min) before reduction.
  • XAS was used to investigate the oxidation state and local chemical structure of the CMO-y catalysts after reduction and after use.
  • Figure 8a shows Co K-edge XANES spectra for CMO-y catalysts after reduction (A) and converted CMO-y catalysts (B), and Figure 8b shows Co K-edge XANES profiles evaluated from linear combination fitting.
  • 8c is a graph showing the relationship between metallic Co content and C 5+ hydrocarbon yield
  • FIG. 8c is a relationship between surface carbide content and C 5+ hydrocarbon yield evaluated from C 1s XPS spectrum (D) and [CoO +CO3O4]/CoO and the graph showing the relationship (E) between the C 5+ hydrocarbon yield
  • the Co 3 O 4 crystal size (5.9 nm) in the CMO-10 catalyst before reduction is smaller than the Co 3 O 4 crystal size (9.7 nm) in the CMO-0 catalyst before reduction. significantly smaller, from which it can be seen that the Mn promoter inhibits the growth of Co 3 O 4 crystals during heat treatment to reduce their size.
  • the reduced CMO-0 catalyst and the reduced CMO-10 catalyst it was found to contain hcp Co and fcc Co phases with similar crystal sizes (20-23 nm).
  • the crystallite sizes of hcp Co and fcc Co were significantly increased to 27.0 nm and 34.5 nm, respectively, in the converted CMO-0 catalyst.
  • the crystallite size of hcp Co and fcc Co slightly increased to 23.4 nm and 21.4 nm, respectively, compared to the CMO-10 catalyst after reduction. From this, it can be seen that the Mn promoter included in the CMO-10 catalyst inhibits the crystal growth of metal Co during the hydrogenation of CO 2 .
  • the Co K-edge XANES spectrum of the reduced CMO-0 catalyst was similar to the standard metallic Co, indicating almost complete reduction from Co 3 O 4 to the metallic Co phase, from which the Mn promoter contained in the catalyst was reduced to Co 3 O It can be further confirmed that the complete reduction of 4 to metal Co is inhibited.
  • the Mn-promoters in CMO-y catalysts can suppress the reduction of Co.
  • the low reducibility of the Mn-rich CMO-y catalyst is due to the increased formation of spinel structure Co x Mn 3-x O 4 as the Mn-content increases.
  • the C 5+ hydrocarbon yield was maximized at a carbide area ratio of 14.7% and a [CoO+Co 3 O 4 ]/Co O ratio of 1.7.
  • some fractions of Co 2 C and CoO x are required to be present on the catalyst surface in order for the FTS reaction to be established in CO 2 hydrogenation.
  • FIG. 9a shows normalized Co K-edge XANES spectra measured for a converted CMO-0 catalyst (A) and a converted CMO-10 catalyst (B) at various reaction pressures (1 MPa, 2 MPa, 3 MPa, 4 MPa), respectively.
  • D Co K-edge XANES spectra measured for the converted CMO-10 catalyst, respectively, and FIG.
  • FIG. 10 shows the k 3 - weighted Fourier transform (k 3 - weighted Fourier transforms, FTs) (A) and CMO-10 catalyst converted at 270 °C fitted only with metallic Co (B), CMO-10 converted at 290 °C catalyst fitted only with metallic Co (C) and metallic Co Filtered K 3 -weighted ⁇ (k) spectra of the CMO-10 catalyst (D) converted at 310 °C fitted with CoO and Normalized Mn K-edge XANES spectra of CMO-y catalyst (A) and converted CMO-y catalyst (B) are shown.
  • k 3 - weighted Fourier transforms, FTs k 3 - weighted Fourier transforms, FTs
  • Table 4 shows the results of linear combination fitting of Mn K-edge XANES profiles for the CMO-y catalyst after reduction and the converted CMO-y catalyst
  • Table 5 shows the results of the linear combination fitting of the CMO-y catalyst after reduction and the converted CMO-y catalyst.
  • the peak at 2.50 ⁇ corresponds to the Co—Co bond of hcp Co.
  • Two additional peaks at 2.14 and 3.30 ⁇ were observed for the CMO-10 catalyst after reduction, and these peaks correspond to Co-O and Co-Co bonds in CoO, respectively.
  • the Co K-edge EXAFS spectrum of the converted CMO-10 catalyst showed one prominent peak centered at 2.50 ⁇ , which is related to the Co-Co bond of hcp Co.
  • FIG. 12 shows CMO-10 catalyst before reduction, CMO-10 catalyst after reduction, and conversion (125 hr, 1425 hr) CMO in C 1s (A), Co 2p (B), O 1s (C) and Mn 2p (D) regions.
  • 13 shows high-resolution XPS profiles of -10 catalysts, and FIG. 13 shows CMO-0 catalyst before reduction, CMO-0 catalyst after reduction and conversion (125 hr) in the C 1s (A), Co 2p (B) and O 1s (C) regions. ) high-resolution XPS profiles of the CMO-10 catalyst.
  • the converted CMO-10 catalyst after the reaction proceeded for 125 hours showed a new peak at 283.2 eV corresponding to Co 2 C. From this, it can be seen that in the initial state of the reaction, Co 2 C was formed on the Co surface by surface carbon species decomposed from adsorbed CO 2 species. As the reaction time increased from 125 hours to 1425 hours, the area ratio of Co 2 C in the converted CMO-10 catalyst increased from 14.7% to 29.1%.
  • two main peaks at 529.6 and 531.2 eV may correspond to lattice oxygen and oxygen vacancies of the metal oxide, respectively.
  • the area ratio of peaks related to oxygen vacancies in the converted CMO-10 catalyst increased from 26.8% (CMO-10 catalyst after reduction) to 53.4% (converted CMO-10 catalyst after 1425 hours reaction).
  • the main Mn species was Mn 2+ .
  • 14a is a diagram showing FE-SEM images (A, B), HR-TEM images (C, D), and particle size distribution (E) of the CMO-0 catalyst before reduction, and FIG. HAADF-STEM image of 0 catalyst (F) and its corresponding Co (G); O (H); C (I); Na(J); Co and O (K); It is a diagram showing EDX images of Co, C and O (L).
  • 15a is a view showing FE-SEM images (A, B), HR-TEM images (C, D), and particle size distribution (E) of the CMO-10 catalyst before reduction, and FIG.
  • 16a is a diagram showing FE-SEM images (A, B), HR-TEM images (C, D), and particle size distribution (E) of the CMO-0 catalyst after reduction, and FIG. HAADF-STEM image of 0 catalyst (F) and its corresponding Co (G); O (H); C (I); Na(J); Co and O (K); It is a diagram showing EDX images of Co, C and O (L).
  • Figure 17a is a diagram showing FE-SEM images (A, B), HR-TEM images (C, D), and particle size distribution (E) of CMO-10 catalyst after reduction
  • Figure 17b is a diagram showing CMO-10 catalyst after reduction HAADF-STEM image of 10 catalyst (F) and its corresponding Co (G); O (H); C (I); Mn (J); Na(K); Co and O (L); It is a diagram showing EDX images of Co, C and O (M).
  • 18a shows HR-TEM images (AC, E) and FFT images (D) of the converted CMO-0 catalyst, and FIG.
  • FIG. 18B shows HAADF-STEM images (F) of the converted CMO-0 catalyst and the corresponding Co ( G); O (H); C (I); Co and O (J); Co, O and C (K); and EDX images of Na (L),
  • FIG. 18C shows Co (M); Co and O (N); An enlarged outermost shell layer of Co, O and C(O) is shown.
  • 19a shows HR-TEM images (AC, E) and FFT images (D) of the converted CMO-10 catalyst, and FIG.
  • FIG. 19B shows HAADF-STEM images (F) of the converted CMO-10 catalyst and the corresponding Co ( G); O (H); C (I); Mn (J); Co, Mn and O (K); and EDX images of Co, Mn, C, and O (L)
  • FIG. 19C shows Co (M); Co and O (N); An enlarged outermost shell layer of Co, O and C(O) is shown.
  • 20 shows N 2 adsorption-desorption contours of the pre-reduction CMO-y catalyst (A), the post-reduction CMO-y catalyst (B), and the converted CMO-y catalyst (C).
  • the CMO-0 catalyst before reduction showed spherical Co 3 O 4 nanoparticles with an average diameter of 9.0 nm.
  • HAADF-STEM high-angle annular dark-field STEM
  • EDX images showed that Na was uniformly distributed over the entire catalyst.
  • the average diameter of the Co 3 O 4 nanoparticles was 5.1 nm, which was reduced compared to that of the CMO-0 catalyst before reduction.
  • the BET surface area of the CMO-10 catalyst before reduction (185.3 m 2 /g) was found to be significantly larger than that of the CMO-0 catalyst before reduction (103.5 m 2 /g). And the BET surface areas of the CMO-25 catalyst before reduction and the CMO-50 catalyst before reduction increased to 214.1 and 210.5 m 2 /g, respectively. Therefore, it can be seen that Mn included in the CMO-y catalyst inhibited the aggregation of internal particles during heat treatment.
  • the average particle diameter of the reduced CMO-0 catalyst increased significantly to 224 nm.
  • the particle growth was inhibited by the Mn promoter during reduction, and as a result, the average particle diameter (18.4 nm) of the CMO-10 catalyst after reduction was about 10 times larger than that of the CMO-0 catalyst after reduction. It was small. Mn and Na species were uniformly distributed on the CMO-10 catalyst after reduction.
  • the Na content was measured to be 0.11 and 0.12 wt%, respectively.
  • the interlayer spacing was in the range of 2.44–2.56 ⁇ , which is due to the presence of oxygen vacancies in the lattice-extended (311) plane of Co 3 O 4 (2.44 ⁇ ) and CoO (2.46 ⁇ ). is consistent with the (111) plane of HAADF-STEM images and corresponding EDX images showed that oxygen and carbon species covered the surface of the metallic Co particles. Closer examination of the EDX images of Co revealed that a dense metallic Co phase in the core and a highly porous Co phase in the shell layer coexist in the catalyst.
  • the porous Co phase was found to overlap O and C elements, indicating that an oxygen- and carbon-rich shell with a thickness of 10 to 15 nm was formed on the surface of the metallic Co core.
  • a carbon layer with a thickness of about 5 nm was observed, which was formed by the FTS reaction. That is, the carbon layer was deposited on the outermost surface of the converted CMO-0 catalyst, and the CoO x and Co 2 C phases were present almost on the surface area.
  • the converted CMO-0 catalyst was Co@Co 2 C/CoO x It was confirmed to have a core-shell structure. However, in some parts of the converted CMO-0 catalyst, the Co 2 C/CoO x shell layer was not uniform, and carbon-rich phases desorbed from the catalyst surface were observed.
  • the particle size of the converted CMO-10 catalyst was found to be increased to almost 100 nm, indicating that interparticle agglomeration occurred during CO 2 hydrogenation.
  • the particle size of the converted CMO-10 catalyst was much smaller compared to the converted CMO-0 catalyst, indicating that the Mn promoter inhibited particle aggregation during CO 2 hydrogenation.
  • the converted CMO-10 catalyst was found to have an hcp Co core and a CoO x /Co 2 C shell structure.
  • the amount of Co oxide detected through the bulk analysis technique (XRD and XAS) was extremely small, while the amount of Co oxide detected through the surface detection technique (XPS) was quite large, It can be seen that the Co oxide species observed in the EDX images are mostly present on the outermost surface of the metal Co core.
  • the Mn promoter inhibited the formation of a carbon-rich layer on the outermost surface of the CMO-10 catalyst, and isolated carbon-rich sheets separated from the catalyst surface. This is due to the formation of a uniform CoO x /Co 2 C shell layer on the surface of the metal Co core nanoparticles.
  • FIG. 21 shows HR-TEM images of the converted CMO-0 catalyst converted under the reaction pressure condition of 1.0 MPa
  • FIG. 22 shows HR-TEM images of the converted CMO-10 catalyst converted under the reaction pressure condition of 1.0 MPa.
  • the thickness of the shell layer present in the converted CMO-0 catalyst converted at a reaction pressure of 1.0 MPa was about 5 nm, which is the thickness of the CMO-0 converted at a reaction pressure of 4.0 MPa. It was considerably thinner than the thickness of the shell layer of the catalyst (10-15 nm).
  • the surface layer of the converted CMO-0 catalyst converted at 1.0 MPa has a higher [CoO+Co 3 O 4 ]/Co 0 ratio (3.1%) and smaller carbide area than that of the converted CMO-0 catalyst converted at 4.0 MPa. The ratio (3.0%) is shown.
  • the metal Co content of the converted CMO-0 catalyst converted at 1.0 MPa (89.1%) was significantly lower than that of the converted CMO-0 catalyst converted at 4.0 MPa (98.6%).
  • the cuboid-shaped Co 2 C particles with a size of about 5 nm are the size of the metal Co particles. formed on the surface. This indicates that the Mn promoter promotes the formation of Co 2 C. However, the formation of cuboid-shaped Co 2 C particles did not increase the C 5+ hydrocarbon yield. Similar to the case of the CMO-0 catalyst, the converted CMO-10 catalyst converted at 1.0 MPa has a higher [CoO+Co 3 O 4 ]/Co 0 ratio ( 2.1), higher carbide area ratio (20.6%) and lower metal Co content (83.5%). From this, it can be seen that the abundant Co oxide and Co 2 C phases in the catalyst formed at low pressure negatively affect the C5+ hydrocarbon yield.
  • the cuboid-shaped Co 2 C particles were formed at a low reaction temperature of 230 °C. As the reaction temperature increased to 250 °C, the Co 2 C cuboid morphology disappeared, and instead a shell layer of about 4 nm thickness formed of a mixture of Co 2 C and CoO x was formed to cover the metallic Co core. At a reaction temperature of 270 °C, the thickness of the shell layer (10-15 nm) increased. In the case of the CMO-10 catalyst converted at a reaction temperature of 310 °C, a rapid morphology change was observed. At a reaction temperature of 310 °C, severe intergranular aggregation between adjacent Co nanoparticles could lead to separation of the carbon-rich layer.
  • Figure 23a shows SEM, HR-TEM and FFT images of the converted CMO-10 catalyst converted under reaction temperature conditions of 230 °C (A), 250 °C (B), 290 °C (C) and 310 °C (D)
  • Figure 23b is HR-TEM of the converted CMO-10 catalyst converted under reaction temperature conditions of 230 °C (A), 250 °C (B), 270 °C (C), 290 °C (D) and 310 °C (E, F) 24 shows SEM, HR-TEM and FFT images of the converted CMO-10 catalyst converted under conditions of H 2 /CO 2 ratios of 1:1, 2:1 and 4:1, and FIG. SEM and HR-TEM images of the CMO-10 catalyst after 1425 hours of reaction are shown.
  • Figure 26a shows the H 2 -TPR profile for the CMO-y catalyst before reduction heat treatment at 330 ° C
  • FIGS. 26b to 26d show the CO 2 -TPD profile, CO-TPD profile and H 2 of the CMO-y catalyst after reduction.
  • Table 6 shows the phase and composition of the peak of the H 2 -TPR profile for the CMO-y catalyst before reduction
  • Tables 7 to 9 show the CO 2 -TPD data, CO-TPD data, and H 2 -TPD data.
  • the amounts of CO 2 , CO and H 2 desorbed from the CMO-y catalyst calculated using each are shown respectively.
  • Amount of desorbed CO (mmol g -1 ) Catalyst Weak ⁇ 250 °C Medium 250-600°C Strong >600 °C Total CMO-0 0.009 0.006 0.004 0.019 CMO-10 0.074 0.053 0.028 0.155 CMO-25 0.106 0.123 0.017 0.246 CMO-50 0.191 0.208 0.069 0.468 CMO-75 0.018 0.042 0.144 0.204
  • the high-temperature peaks at 427-470° C. for the CMO-y catalysts (10 ⁇ y ⁇ 75) show that the spinel structure of Co x Mn 3-x O 4 is Indicates that the reducing properties of the catalyst are hindered.
  • the reduction temperature of Co 3 O 4 to CoO increased from 258 °C (CMO-0) to 345 °C (CMO-75), indicating that the presence of Mn inhibits the reduction of cobalt oxide.
  • the presence of Mn increased the adsorption of CO 2 and CO, but decreased the adsorption of H 2 .
  • strong adsorption for CO and CO 2 and weak adsorption for H 2 on CMO-y catalysts containing Mn can increase the C/H surface coverage ratio and thus increase the FTS rate across methanation. can help to improve CO 2 conversion and C 5+ hydrocarbon selectivity.
  • DRIFT spectra were collected during pressurization of the DRIFT cell from 0.1 MPa to 3.0 MPa with CO 2 to identify species of intermediate products derived from CO 2 adsorbed on the surface of the catalyst, at which time the DRIFT cell was operated at 350 °C. contained a previously H 2 -reduced CMO-0 catalyst.
  • FIGS. 27A to 27D show in situ DFIFT CO 2 adsorption profiles on CMO-10 catalyst
  • FIGS. 28A to 28C show in situ DFIFT CO 2 adsorption profiles on CMO-0 catalyst
  • FIGS. 29A to 29C show In situ DFIFT CO adsorption profiles on CMO-0 catalyst are shown
  • FIGS. 30A-30C show in situ DFIFT CO adsorption profiles on CMO-10 catalyst
  • FIGS. 31A and 31B show CO pressurization to 3.0 MPa and 270° C.
  • FIGS. 32A to 32C show reaction profiles of in situ DFIFT CO 2 and H 2 on CMO-0 catalyst after reduction
  • FIGS. 33A to 33C show reaction profiles of in situ DFIFT CO 2 and H on CMO-10 catalyst after reduction.
  • FIGS. 34A and 34B show in situ DFIFT CO 2 and H 2 reaction profiles (A) for 60 minutes over CMO-10 catalyst after reduction under varying reaction pressure conditions and CO 2 during hydrogenation of CO 2 - Evolution of adsorbed species, adsorbed CO, gaseous CO and CH 4 (B)
  • FIGS. 35A and 35B show in situ DFIFT CO over 60 min over CMO-0 catalyst after reduction under varying reaction temperature conditions.
  • A is the result measured while increasing the temperature to 270° C. after pressurizing the cell to 3.0 MPa with CO 2
  • B is caused by switching the gas flow from CO 2 to H 2 is the result measured during hydrogenation of the CO 2 -adsorbed species
  • C represents the evolution of the selected CO 2 -adsorbed species
  • CO and CH 4 during hydrogenation
  • D is the QMS profile of the product released from the DRIFT cell under H 2 flow conditions.
  • B is the result obtained by converting the gas flow from CO to H 2 Results measured during hydrogenation of the resulting CO-adsorbing species
  • C represents the evolution of selected CO 2 -adsorbing species, CO and CH 4 during hydrogenation.
  • 32A to 32C and 33A to 33C A is the measured result during CO 2 and H 2 injection at a pressure of 3.0 MPa and a temperature of 270° C.
  • B is the gas flow from CO 2 /H 2 to H 2 Results measured during the H 2 flow induced by conversion
  • C represents the evolution of selected CO 2 -adsorbing species, CO and CH 4 during hydrogenation.
  • CH 4 formation on the reduced CMO-0 catalyst indicates that the CO 2 methanation reaction has occurred due to pre-adsorbed H 2 remaining after reduction.
  • the IR bands associated with CH 4 and ⁇ CH decreased because the H 2 previously adsorbed on the catalyst surface was gradually consumed.
  • the pressure in the DRIFT cell was increased to 3.0 MPa. Then, while maintaining the pressure of the cell at 3.0 MPa, the temperature of the cell was increased to 270°C.
  • the intensity of the IR spectrum under the conditions of 270°C and 3.0 MPa was very similar to that under the conditions of 50°C and 3.0 MPa.
  • peaks at 1577, 1374 and 1362 cm -1 can be assigned to ⁇ as (OCO), ⁇ (CH), and ⁇ s (OCO) of formate (HCOO - ) .
  • the intensity of the IR bands of 2- , HCOO - , [Co ⁇ + -(CO)], CO gas and CH 4 decreased.
  • m-CO 3 2- and HCOO- peaks had minimum intensity in the initial 30 min H 2 flow, and peaks of CO gas and CH 4 were observed in the 40 min H 2 flow.
  • the changes in IR band intensities of m-CO 3 2- , HCOO - , CO and CH 4 were different from each other; [Co ⁇ + -(CO)] and CO gas reached maximum intensity at 90 min of H 2 flow and decreased to near zero as the H 2 flow time was further increased.
  • Quadrupole mass spectrometry (QMS) profiles of products released from the DRIFT cell during H 2 flow show the formation of CO and H 2 O by RWGS reaction and CH 4 , C 2 H 6 and C 3 by FTS on CMO-10 catalyst. Indicates the formation of H 5 .
  • DRIFTS spectra as the pressure in the DRIFT cell was increased from 0.1 MPa to 3.0 MPa were collected by flowing CO to characterize the intermediate species derived from the adsorption of CO on the surface of the catalyst, wherein the DRIFT cell was preheated at 350 °C. It contained H 2 -reduced CMO-0 catalyst. Unlike CO 2 adsorption, no formation of CH 4 was observed during CO adsorption, indicating that direct hydrogenation of CO to CH 4 does not occur under H 2 deficient conditions.
  • CH 4 formation during pressurization of CO 2 over the previously H 2 -reduced CMO-0 catalyst indicates that direct hydrogenation of CO 2 to CH 4 occurred without passing CO, and under H 2 -starved conditions It indicates that surface adsorbed CO species are not precipitated in the methanation reaction.
  • the CO 2 peaks at 2333 and 2364 cm ⁇ 1 were prominent during the initial 15 min of CO adsorption, indicating the high WGS activity of the CMO-0 catalyst.
  • the temperature increased from 50 °C to 270 °C
  • the peaks associated with CO 2 increased due to the increase in WGS reaction activity with increasing temperature.
  • the gas flow through the DRIFT cell was switched from CO to H 2 under conditions of 270° C.
  • the CO adsorption and hydrogenation behavior of the adsorbed CO on the CMO-10 catalyst was similar to that on the CMO-0 catalyst.
  • the main difference is the WGS activity in the initial 5 minutes of CO flow, the intensity of gaseous CO 2 reaches a maximum on the CMO-10 catalyst, which is significantly faster than on the CMO-0 catalyst.
  • Both gaseous CO 2 and CO were present at the end of the temperature ramp from 3.0 MPa to 270 °C.
  • the formation of H 2 O by RWGS over the CMO-10 catalyst was more pronounced than over the CMO-0 catalyst.
  • the H 2 partial pressure was increased compared to that over the CMO-0 catalyst, the more abundant CO produced by RWGS over the CMO-10 catalyst promoted the formation of C 2 H 6 followed by the formation of CH 4 .
  • CMO-y catalysts are mixtures of metallic Co, Co-carbide and Co-oxide phases, which can modify reaction intermediates, so that it is necessary to characterize their respective role in the CO 2 conversion by decoupling of each phase. do.
  • the atomic level mechanism of CO 2 hydrogenation on Co (001), Co 2 C (101) and Co 3 O 4 (110) surfaces was investigated using DFT calculations.
  • Co 3 O 4 was selected as a representative structure of Co-oxide, and the mechanism was comparatively analyzed. Also, the effect of surface oxygen vacancies (vac-Co 3 O 4 (110)) on Co 3 O 4 on the catalytic energetics was investigated.
  • 36 shows the CO 2 hydrogenation pathway (A), the surface structure of Co-containing phases (B), and the free energies of CO 2 hydrogenation (C, D) for CH and CO under conditions of a temperature of 270 °C and a pressure of 4.0 MPa.
  • 37 shows the free energy profiles (A, B) calculated by DFT of the RWGS reaction through HCOO intermediates and HOCO intermediates and the free energy profile of CO hydrogenation to CH formation (C). (* indicates surface-bound species)
  • initial CO 2 activation proceeded by the formation of three different intermediates, HCOO*, COOH*, and CO*.
  • HCOO* pathway continuous oxygen removal resulted in the formation of CH*, which served as a precursor for FTS and methanation.
  • HCOO* on Co 3 O 4 and oxygen-deficient Co 3 O 4 (vac-Co 3 O 4 ) surfaces is advantageous because it has small mechanical barriers of 0.73 and 0.97 eV.
  • the subsequent oxygen removal of HCOO* to produce HCO* and CH* occurs on vac-Co 3 O 4 , where the kinetic barrier is significantly smaller than that of Co 3 O 4 .
  • the HCOO*-species shown in the DRIFT spectrum are present on the outermost CO oxide surface, and they can be readily converted to CHO* and CH* at adjacent oxygen vacancies. As shown in Fig.
  • Co oxide phases are active sites for the RWGS reaction to proceed through direct cleavage of OC-O bonds.
  • the RWGS route through the HOCO* intermediate was not favorable because of the high activation barrier that occurred regardless of the Co phase.
  • the high yield of C5+ hydrocarbons on the CMO-0 and CMO-10 catalysts is due to the activated FTS reaction on the hcp Co site.
  • the thermodynamic limitations of RWGS e.g., CO 2 conversion of about 18% at 270 °C and H 2 /CO 2 ratio of 3
  • promote continuous CO consumption by the C-C coupling reaction on the metallic Co center can be overcome by Little CO was observed in the product stream during CO 2 hydrogenation, except under low pressure conditions where methanation reactions were predominantly observed.
  • the evolution of CO and CO 2 during CO 2 adsorption and CO 2 hydrogenation and in the DRIFT profiles during CO hydrogenation indicate that the CMO-0 and CMO-10 catalysts are highly active for both RWGS and WGS reactions.
  • the negligible amount of CO in the product is due to the rapid conversion of CO on the hcp Co metal center.
  • the produced CO then migrated to the metallic Co centers in the Co 2 C phase and nearby cores, where the active chain propagation reaction takes place.
  • Mn sufficiently enhanced CO 2 conversion and C 5+ hydrocarbon selectivity.
  • the Mn promoter effectively inhibited particle aggregation during CO 2 hydrogenation, which further enhanced CO 2 adsorption and RWGS response.
  • the IR band of the linearly adsorbed CO was not red-shifted on the CMO-10 catalyst (which was previously observed for Mn-promoted Co/TiO 2 and Co-Mn) and was not empty.
  • the significantly larger metal Co size in the delayed CMO-10 catalyst can minimize the electron donor effect from MnCO 3 to metal Co in the CO adsorption state.
  • Mn facilitated the formation of the CoO x /Co 2 C shell layer, which further activated the RWGS reaction.
  • the high yield of C5+ hydrocarbons on the CMO-10 catalyst means that the moderate reaction temperature (270 °C) and high reaction pressure (4.0 MPa) of the metal Co core of the Co@CoO x /Co 2 C catalyst Indicates that it helps to maintain metallic properties.
  • the catalyst's long-term stability, high selectivity towards gas/liquid fuels and lube base oil, and low temperature synthesis conditions make Mn-promoted core-shell Co@CoO x /Co 2 C catalysts suitable for use in CO 2 under industrially relevant conditions. can make it promising.
  • Catalysts according to embodiments of the present invention may be used for hydrogenation of carbon dioxide.

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Abstract

Un catalyseur permettant d'accélérer l'hydrogénation de dioxyde de carbone est divulgué. Le catalyseur peut comprendre un cœur comportant une phase de cobalt métallique, et une écorce positionnée sur la surface du cœur et comprenant une phase de Co3O4 et une phase de Co2C.
PCT/KR2023/002822 2022-02-28 2023-02-28 Catalyseur de synthèse de composé hydrocarboné par réaction directe entre du dioxyde de carbone et de l'hydrogène, procédé de préparation associé et procédé de synthèse de composé hydrocarboné utilisant ledit catalyseur WO2023163573A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109158107A (zh) * 2018-08-17 2019-01-08 中国科学院化学研究所 一种由二氧化碳直接加氢制备液体烃的方法
KR20210079068A (ko) * 2019-12-19 2021-06-29 재단법인 포항산업과학연구원 탄화수소 제조용 촉매 및 이의 제조 방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109158107A (zh) * 2018-08-17 2019-01-08 中国科学院化学研究所 一种由二氧化碳直接加氢制备液体烃的方法
KR20210079068A (ko) * 2019-12-19 2021-06-29 재단법인 포항산업과학연구원 탄화수소 제조용 촉매 및 이의 제조 방법

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JO, H ET AL.: "Unraveling the role of cobalt in the direct conversion of CO2 to high-yield liquid fuels and lube base oi l", APPLIED CATALYSIS B: ENVIRONMENTAL, vol. 305, no. 121041, 24 December 2021 (2021-12-24), pages 1 - 15, XP086939721, DOI: 10.1016/j.apcatb.2021.121041 *
MELAET GÉRÔME, RALSTON WALTER T., LI CHENG-SHIUAN, ALAYOGLU SELIM, AN KWANGJIN, MUSSELWHITE NATHAN, KALKAN BORA, SOMORJAI GABOR A.: "Evidence of Highly Active Cobalt Oxide Catalyst for the Fischer–Tropsch Synthesis and CO 2 Hydrogenation", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 136, no. 6, 12 February 2014 (2014-02-12), pages 2260 - 2263, XP093087478, ISSN: 0002-7863, DOI: 10.1021/ja412447q *
YIN, G ET AL.: "Efficient Reduction of C02 to CO Using Cobalt-Cobalt Oxide Core-Shell Catalysts", CHEM. EUR. J., vol. 24, 2018, pages 2157 - 2163, XP071848436, DOI: 10.1002/chem.201704596 *
ZHAO ZIANG, LU WEI, YANG RUOOU, ZHU HEJUN, DONG WENDA, SUN FANFEI, JIANG ZHENG, LYU YUAN, LIU TAO, DU HONG, DING YUNJIE: "Insight into the Formation of Co@Co 2 C Catalysts for Direct Synthesis of Higher Alcohols and Olefins from Syngas", ACS CATALYSIS, AMERICAN CHEMICAL SOCIETY, US, vol. 8, no. 1, 5 January 2018 (2018-01-05), US , pages 228 - 241, XP093087480, ISSN: 2155-5435, DOI: 10.1021/acscatal.7b02403 *

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